Patent Application
20240106060
This application relates to the field of lithium-ion batteries, and in particular, to a battery pack having a high energy retention rate under low temperature and an electric apparatus including such battery pack.
In recent years, with the continuous development of lithium-ion battery technologies, lithium-ion batteries have been widely used in energy storage power supply systems such as hydroelectric, thermal, wind, and solar power plants, as well as many other fields including electric tools, electric bicycles, electric motorcycles, electric vehicles, military equipment, and aerospace.
In the foregoing fields, the capacity of a lithium-ion secondary battery cell sometimes cannot meet use demands. Therefore, it is needed to connect a plurality of lithium-ion secondary battery cells in series or in parallel to form a battery pack to increase the overall discharge capacity of the battery pack.
However, when a battery pack formed by lithium-ion secondary battery cells is used in a low-temperature environment, for example, in winter, the energy retention rate is significantly reduced, that is, the endurance under low temperature is significantly reduced. Therefore, how the overall endurance of the battery pack under low temperature is improved has become a key problem to be resolved urgently.
This application is made in view of the foregoing technical problem and is intended to provide a battery pack formed by lithium-ion secondary batteries that has an excellent energy retention rate and improved endurance under low temperature, as well as an electric apparatus including such battery pack.
To achieve the foregoing purpose, a first aspect of this application provides a battery pack including a battery pack box and a battery cell accommodated in the battery pack box. The battery pack is characterized in that
In this application, the temperature distribution in the internal space of the battery pack can be determined using a simulation method. Subsequently, the internal space of the battery pack box is divided into n regions according to a descending order of temperature.
In an example, the temperature distribution in the internal space of the battery pack can be determined using a simulation method with ANSYS-SCDM software (Beijing Huanzhong Ruichi Technology Co., Ltd.). The method includes the following steps.
In any embodiment, based on the determined temperature distribution in the entire internal space of the battery pack box during use under low temperature, for the first region or the k-th region, a difference between a maximum temperature and a minimum temperature in a same region is greater than or equal to 3° C., optionally, less than or equal to 10° C.
Optionally, the maximum temperature in the k-th region is less than or equal to a minimum temperature in the (k−1)-th region.
When the difference between the maximum temperature and the minimum temperature in space of the battery pack box is less than 3° C., region division may not be required. It can be learned from experience that a temperature difference of less than 3° C. in a same region has little influence on the discharge capacity of the battery in this region.
In any embodiment, in the entire internal space of the battery pack box, based on the determined temperature distribution in the internal space of the battery pack box during use under low temperature, a maximum temperature is TH, a minimum temperature is TL, and TH−TL=TM.
When TM≥6° C., optionally when TM≥7° C., n≥2,
Optionally, the inside of the battery pack box may be divided into two regions, three regions, or four regions; at most five regions; and in some embodiments three regions.
In any embodiment, the internal space of the battery pack box is divided into three regions. As shown in
Further, a first battery cell 61 is provided in the first region R1, a second battery cell 62 is provided in the second region R2, and a third battery cell 63 is provided in the third region R3. The second battery cell 62 is arranged around the first battery cell 61, and the third battery cell 63 is arranged around the second battery cell 62. The first battery cell 61, the second battery cell 62, and the third battery cell 63 each have a first discharge voltage plateau and a second discharge voltage plateau. An average discharge voltage of the first discharge voltage plateau is higher than an average discharge voltage of the second discharge voltage plateau. Respective positive electrode active substances of the first battery cell 61, the second battery cell 62, and the third battery cell 63 each are formed by mixing lithium iron phosphate and/or lithium nickel cobalt manganate having a first discharge voltage plateau, and a supplementary active substance having a second discharge voltage plateau. In the first battery cell 61, the second battery cell 62, and the third battery cell 63, in any case where a sum of a discharge capacity corresponding to the first discharge voltage plateau and a discharge capacity corresponding to the second discharge voltage plateau is 100%, a discharge capacity proportion corresponding to the second discharge voltage plateau of the third battery cell 63>a discharge capacity proportion corresponding to the second discharge voltage plateau of the second battery cell 62>a discharge capacity proportion corresponding to the second discharge voltage plateau of the first battery cell 61. When placed in an external environment at a same temperature, after a battery has run for a specified time, in a battery pack 1, the third region R3 has a lower temperature than the second region R2, and the second region R2 has a lower temperature than the first region R1.
Battery cells with different low-temperature energy retention rates and having double discharge voltage plateaus (a first discharge voltage plateau having a higher discharge voltage and a second discharge voltage plateau having a lower discharge voltage) are respectively provided in different regions of the battery pack box. In addition, a battery cell with a higher low-temperature energy retention rate is provided in a region at a lower temperature. Specifically, region division in
The above principle is also applicable to low-temperature energy retention of the battery pack including a k-th battery cell.
In this application, the supplementary active substance of which the molecular formula is AxMy(PO4)z can serve as a plateau attenuation buffer agent and can slow down decrease of a discharge voltage when a terminal voltage of a cell during discharging attenuates sharply, thereby prolonging the discharging process and improving the discharging power performance.
In any embodiment, a positive electrode active substance of the first battery cell 61 has a gram capacity of 140-198 mAh/g, a positive electrode active substance of the second battery cell has a gram capacity of 137-192 mAh/g, and a positive electrode active substance of the third battery cell has a gram capacity of 134-186 mAh/g.
In this way, the respective gram capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 being within the foregoing ranges allows for substantially same discharge capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 under low temperature, thereby increasing the overall energy retention rate of the battery pack 1 under low temperature.
In any embodiment, the supplementary active substance is one or more selected from Li3V2(PO4)3, Na3V2(PO4)3, K3V2(PO4)3, Li3V(PO4)2, Na3V(PO4)2, K3V(PO4)2, LiMnPO4, NaMnPO4, KMnPO4, Li2VMn2(PO4)3, Na2VMn2(PO4)3, K2VMn2(PO4)3, LiVMn(PO4)2, NaVMn(PO4)2, KVMn(PO4)2, CaV4(PO4)6, LiTi2(PO4)3, NaTi2(PO4)3, KTi2(PO4)3, CaTi4(PO4)6, Li2VTi(PO4)3, Na2VTi(PO4)3, K2VTi(PO4)3, CaVTi(PO4)3, Li3MnTi(PO4)3, Na3MnTi(PO4)3, and K3MnTi(PO4)3.
In any embodiment, in the positive electrode of each k-th battery cell, a mass percentage of the supplementary active substance is 3% to 15% based on a total mass of the positive electrode active substance.
If the mass percentage of the supplementary active substance is less than 3%, the discharge voltage plateau thereof cannot be shown in a discharge curve, that is, cannot achieve a power increasing effect. If the mass percentage of the supplementary active substance is greater than 15%, the energy retention rate thereof under low temperature is still increased. However, a large percentage thereof not only deteriorates the discharge capacity under room temperature but also results in failure of a more significant increase in overall discharge capacity under low temperature.
In any embodiment, the positive electrode of each first battery cell includes no supplementary active substance, or the positive electrode of each first battery cell includes the supplementary active substance, optionally, a second voltage plateau of the supplementary active substance in the first battery cell is greater than or equal to an overall discharge cut-off voltage of the first battery cell.
In this application, the positive electrode of the first battery cell in the first region may include no supplementary active substance, may partially include the supplementary active substance, or may entirely include the supplementary active substance.
When the first battery cell partially or entirely includes the supplementary active substance, it is advantageous to make the voltage plateau of the supplementary active substance be greater than or equal to the overall discharge cut-off voltage of the first battery cell, because this allows the supplementary active substance to effectively act as a plateau attenuation buffer agent before cutoff of discharging.
In any embodiment, when the respective positive electrodes of the first battery cell to the n-th battery cell include a same positive electrode active substance, a percentage of the supplementary active substance in the positive electrode of the (k−1)-th battery cell is less than or equal to a percentage of the supplementary active substance in the positive electrode of the k-th battery cell.
A larger mass percentage of the supplementary active substance for generating the second discharge voltage plateau with a lower discharge voltage indicates a larger discharge capacity proportion corresponding to the second discharge voltage plateau. Therefore, adding a larger percentage of supplementary active substance into the k-th battery cell than the (k−1)-th battery cell in the k-th region at a lower temperature helps to increase the overall low-temperature energy retention rate of the battery pack.
In any embodiment, the positive electrode of each first battery cell includes no supplementary active substance or includes a same type of supplementary active substance as the second battery cell and the third battery cell.
In any embodiment, in the positive electrode of each first battery cell, a mass percentage of the supplementary active substance is 0% to 3% based on a total mass of the active substance of the positive electrode;
in the positive electrode of each second battery cell, a mass percentage of the supplementary active substance is 3% to 7% based on a total mass of the active substance of the positive electrode; and in the positive electrode of each third battery cell, a mass percentage of the supplementary active substance is 7% to 15% based on a total mass of the active substance of the positive electrode.
In this application, the mass percentages of the supplementary active substances in the first battery cell, the second battery cell, and the third battery cell being within the foregoing ranges can better balance discharge periods of the first battery cell, the second battery cell, and the third battery cell to make the discharge periods be the same as far as possible and can further improve the overall low-temperature energy retention rate and power performance of the battery pack.
In any embodiment, under a temperature below 10° C., 1.6 V≤discharge cut-off voltage of the k-th battery cell≤discharge cut-off voltage of the (k−1)-th battery cell≤2.1 V.
An outer ring (the k-th region) of the battery pack is at a low temperature, and an inner ring (the (k−1)-th region, with respect to the k-th region of the outer ring) is at a high temperature, resulting in a short discharge cut-off time and a smaller discharge capacity as well as power performance degradation of the cell in the outer ring. A lower cut-off voltage of the outer ring can allow for release of more energy, compensating for discharge variation of the cell caused by temperature rise in the battery pack, thereby increasing the overall discharge capacity of the battery pack.
In any embodiment, an overall discharge cut-off voltage V1 of the first battery cell is 2.0-2.1 V, an overall discharge cut-off voltage V2 of the second battery cell is 1.7-2.0 V, an overall discharge cut-off voltage V3 of the third battery cell is 1.6-1.9 V, and V1>V2>V3.
In this way, the discharge cut-off voltages of the first battery cell 61, the second battery cell 62, and the third battery cell 63 being set as described above allows the first battery cell 61, the second battery cell 62, and the third battery cell 63 to release substantially same energy under low temperature, thereby increasing the overall energy retention rate of the battery pack under low temperature.
In any embodiment, a discharge capacity of a single cell of each k-th battery cell is less than a discharge capacity of a single cell of each (k−1)-th battery cell.
In this way, making the discharge capacities of the respective single cells of the first battery cell 61, the second battery cell 62, and the third battery cell 63 satisfy the above relationship, especially making the discharge capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 measured at room temperature, for example, at a temperature of 25° C. satisfy the above relationship can further increase the overall energy retention rate of the battery pack under low temperature.
A second aspect of this application provides a method for arranging battery pack. The battery pack includes a battery pack box and a battery cell accommodated in the battery pack box. The method includes the following steps.
The internal space of the battery pack box includes one or more first regions and/or k-th regions.
A positive electrode of each k-th battery cell includes a positive electrode active substance. The positive electrode active substance includes the following substances:
A third aspect of this application provides an electric apparatus. The electric apparatus includes the battery pack according to the first aspect of this application. The battery pack may be used as a power source of the electric apparatus or an energy storage unit of the electric apparatus. The electric apparatus may include a mobile device (for example, a mobile phone or a notebook computer), an electric vehicle (for example, a battery electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf vehicle, or an electric truck), an electric train, a ship, a satellite system, an energy storage system, or the like, but is not limited thereto.
The following specifically discloses embodiments of a battery pack and an electric apparatus in this application with appropriate reference to detailed descriptions of accompanying drawings. However, there may be cases where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters and repeated descriptions of actually identical structures have been omitted. This is to avoid unnecessarily prolonging the following description, for ease of understanding by persons skilled in the art. In addition, the accompanying drawings and the following descriptions are provided for persons skilled in the art to fully understand this application and are not intended to limit the subject matter recorded in the claims.
“Ranges” disclosed in this application are defined in the form of lower and upper limits. A given range is defined by one lower limit and one upper limit selected, where the selected lower and upper limits define boundaries of that particular range. Ranges defined in this method may or may not include end values, and any combinations may be used, meaning any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are provided for a specific parameter, it is understood that ranges of 60-110 and 80-120 can also be envisioned. In addition, if minimum values of a range are given as 1 and 2, and maximum values of the range are given as 3, 4, and 5, the following ranges can all be envisioned: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-6. In this application, unless otherwise stated, a value range of “a-b” is a short representation of any combination of real numbers between a and b, where both a and b are real numbers. For example, a value range of “0-5” means that all real numbers in the range of “0-5” are listed herein, and “0-5” is just a short representation of a combination of these values. In addition, a parameter expressed as an integer greater than or equal to 2 is equivalent to disclosure that the parameter is, for example, an integer of 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12. The value ranges “a-b” and “a to b” are used with the same meanings.
Unless otherwise specified, all the embodiments and optional embodiments of this application can be combined with each other to form new technical solutions.
Unless otherwise specified, all the technical features and optional technical features of this application can be combined with each other to form new technical solutions.
Unless otherwise specified, all the steps in this application can be performed in the order described or in random order, in some embodiments, in the order described. For example, a method including steps (a) and (b) indicates that the method may include steps (a) and (b) performed in order or may include steps (b) and (a) performed in order. For example, the foregoing method may further include step (c), which indicates that step (c) may be added to the method in any ordinal position, for example, the method may include steps (a), (b), and (c), steps (a), (c), and (b), steps (c), (a), and (b), or the like.
Unless otherwise specified, “include” and “contain” mentioned in this application are inclusive. For example, the terms “include” and “contain” can mean that other unlisted components may or may not also be included or contained.
Unless otherwise specified, in this application, the term “or” is inclusive. For example, the phrase “A or B” means “A, B, or both A and B”. More specifically, any one of the following conditions satisfies the condition “A or B”: A is true (or present) and B is false (or not present); A is false (or not present) and B is true (or present); or both A and B are true (or present).
The inventors have noted that when a battery pack formed by lithium-ion secondary battery cells is used in a low-temperature environment in winter, the battery cells at different positions in the battery pack are different in dissipation capability and heat insulation effect, so the battery cells at different positions have different charge/discharge performance. Specifically, during use in a low-temperature environment, the inner battery cell in the battery pack has a relatively higher temperature and therefore has relatively better discharge performance under low temperature, and the outer battery cell in the battery pack has a relatively lower temperature and therefore has relatively lower discharge performance under low temperature. The battery cells at different positions in the battery pack are different in discharge capability under low temperature, resulting in significant decrease in the overall energy retention rate of the battery pack under low temperature.
In view of the above problem, the inventors have found through repeated research that the battery cells provided in a region at a relatively low temperature each have two discharge voltage plateaus, and after discharging in the discharge voltage plateau having a higher voltage ends, the battery cells continue to be discharged using the discharge voltage plateau having a lower voltage, increasing the discharge capacities of these battery cells, so that these battery cells have better discharge performance under low temperature.
Therefore, a first aspect of this application provides a battery pack including a battery pack box and a battery cell accommodated in the battery pack box. The battery pack is characterized in that
In this application, the temperature distribution in the internal space of the battery pack can be determined using a simulation method. Subsequently, the internal space of the battery pack box is divided into n regions according to a descending order of temperature.
In an example, the temperature distribution in the internal space of the battery pack can be determined using a simulation method with ANSYS-SCDM software. The method includes the following steps.
It should be noted that for this application, the method for determining the temperature distribution in the internal space of the battery pack is not limited to the simulation method. The concept of this application is aimed at addressing the issue of discharge variation of the battery cells at different positions and overall discharge capacity reduction due to temperature distribution variation in the battery pack in actual use under low temperature. Therefore, all methods capable of determining the temperature distribution inside the battery pack in actual application scenarios are within the concept scope of this application.
It can be understood that the internal space of the battery pack box in this application may include one or more, optionally, only one first region and/or k-th region.
In some embodiments, based on the determined temperature distribution in the entire internal space of the battery pack box during use under low temperature, for the first region or the k-th region, a difference between a maximum temperature and a minimum temperature in a same region is greater than or equal to 3° C., optionally, less than or equal to 10° C.
Optionally, the maximum temperature in the k-th region is less than or equal to a minimum temperature in the (k−1)-th region.
When the difference between the maximum temperature and the minimum temperature in space of the battery pack box is less than 3° C., region division may not be required. It can be learned from experience that a temperature difference of less than 3° C. in a same region has little influence on the discharge capacity of the battery in this region.
However, it should be understood that in this application, the difference between the maximum temperature and the minimum temperature in a same region is limited to be greater than or equal to 3° C., optionally less than or equal to 10° C.; however, this solution is merely an option, and the difference between the maximum temperature and the minimum temperature in a same region being less than 3° C. or greater than 10° C. is also within the concept scope of this application.
In some embodiments, in the entire internal space of the battery pack box, based on the determined temperature distribution in the internal space of the battery pack box during use under low temperature, a maximum temperature is TH, a minimum temperature is TL, and TH−TL=TM.
When TM≥6° C., optionally when TM≥7° C., n≥2,
As such, internal regions in the space of the battery pack box can be divided better, and such division manner allows the battery pack to better adapt to a low-temperature environment.
Optionally, TM/n represents a range, that is, a range of (TM/n−3° C.) to (TM/n+3° C.).
In this application, “low temperature” refers to a temperature less than or equal to 10° C.
Optionally, the inside of the battery pack box may be divided into two regions, three regions, or four regions; at most five regions; and in some embodiments three regions.
The following uses a case in which the internal space of the battery pack box is in a substantially rectangular shape as an example to specify the battery pack according to the first aspect of this application. However, the battery pack in this application is not limited to the case in which the internal space of the battery pack box is in a substantially rectangular shape.
As shown in
Under a condition that the internal space of the battery pack box is divided into two regions, as shown in
Further, a first battery cell 61 is provided in the first region R1, a second battery cell 62 is provided in the second region R2, and the second battery cell 62 and the first battery cell 61 are arranged adjacent to each other. In this application, A and B being arranged “adjacent to each other” can be understood as that A surrounds B, B surrounds A, or A and B are arranged adjacent to each other in a single direction. In addition, A and B being arranged “adjacent to each other” also includes a case in which a spacing member (for example, a spacer plate) is present between A and B or no spacing member (for example, a spacer plate) is present between A and B.
The first battery cell 61 and the second battery cell 62 each have a first discharge voltage plateau and a second discharge voltage plateau. An average discharge voltage of the first discharge voltage plateau is higher than an average discharge voltage of the second discharge voltage plateau. Respective positive electrode active substances of the first battery cell 61 and the second battery cell 62 each are formed by mixing lithium iron phosphate and/or lithium nickel cobalt manganate having a first discharge voltage plateau, and a supplementary active substance having a second discharge voltage plateau. In the first battery cell 61 and the second battery cell 62, in any case where a sum of a discharge capacity corresponding to the first discharge voltage plateau and a discharge capacity corresponding to the second discharge voltage plateau is 100%, a discharge capacity proportion corresponding to the second discharge voltage plateau of the second battery cell 62 is greater than a discharge capacity proportion corresponding to the second discharge voltage plateau of the first battery cell 61. When placed in an external environment at a same temperature, in the battery pack 1, the second region R2 has a lower temperature than the first region R1.
The “discharge capacity proportion corresponding to the second discharge voltage plateau” of each battery cell refers to a proportion of the discharge capacity corresponding to the second discharge voltage plateau of each battery cell, calculated based on a total discharge capacity corresponding to the first discharge voltage plateau and the second discharge voltage plateau of each battery cell, where the discharge capacity corresponding to the first discharge voltage plateau and the discharge capacity corresponding to the second discharge voltage plateau of each of the first battery cell 61 and the second battery cell 62 are respectively measured under a same charge/discharge condition at a temperature below 10° C. (for example, −7° C.) before the first battery cell 61 and the second battery cell 62 are assembled into the battery pack.
In addition, under a condition that the internal space of the battery pack box is divided into three regions, as shown in
Further, a first battery cell 61 is provided in the first region R1, a second battery cell 62 is provided in the second region R2, and a third battery cell 63 is provided in the third region R3. The second battery cell 62 is arranged around the first battery cell 61, and the third battery cell 63 is arranged around the second battery cell 62. The first battery cell 61, the second battery cell 62, and the third battery cell 63 each have a first discharge voltage plateau and a second discharge voltage plateau. An average discharge voltage of the first discharge voltage plateau is higher than an average discharge voltage of the second discharge voltage plateau. Respective positive electrode active substances of the first battery cell 61, the second battery cell 62, and the third battery cell 63 each are formed by mixing lithium iron phosphate and/or lithium nickel cobalt manganate having a first discharge voltage plateau, and a supplementary active substance having a second discharge voltage plateau. In the first battery cell 61, the second battery cell 62, and the third battery cell 63, in any case where a sum of a discharge capacity corresponding to the first discharge voltage plateau and a discharge capacity corresponding to the second discharge voltage plateau is 100%, a discharge capacity proportion corresponding to the second discharge voltage plateau of the third battery cell 63>a discharge capacity proportion corresponding to the second discharge voltage plateau of the second battery cell 62>a discharge capacity proportion corresponding to the second discharge voltage plateau of the first battery cell 61. When placed in an external environment at a same temperature, after a battery has run for a specified time, in the battery pack 1, the third region R3 has a lower temperature than the second region R2, and the second region R2 has a lower temperature than the first region R1.
The “discharge capacity proportion corresponding to the second discharge voltage plateau” of each battery cell refers to a proportion of the discharge capacity corresponding to the second discharge voltage plateau of each battery cell, calculated based on a total discharge capacity corresponding to the first discharge voltage plateau and the second discharge voltage plateau of each battery cell, where the discharge capacity corresponding to the first discharge voltage plateau and the discharge capacity corresponding to the second discharge voltage plateau of each of the first battery cell 61, the second battery cell 62, and the third battery cell 63 are respectively measured under a same charge/discharge condition at a temperature below 10° C. (for example, −7° C.) before the first battery cell 61, the second battery cell 62, and the third battery cell 63 are assembled into the battery pack.
It should be particularly noted that throughout the specification of this application, the first battery cell is described as having a first discharge voltage plateau and a second discharge voltage plateau, or the positive electrode active substance of the first battery cell is described as being formed by mixing lithium iron phosphate and/or lithium nickel cobalt manganate having a first discharge voltage plateau, and a supplementary active substance having a second discharge voltage plateau; however, the first battery cell having only the first discharge voltage plateau but no second discharge voltage plateau, that is, the first battery cell formed by only the lithium iron phosphate and/or lithium nickel cobalt manganate is also included in the scope of this application.
It should be noted that the “discharge voltage plateau” refers to a portion in which the discharge voltage is relatively stable in a discharge curve.
Battery cells with different low-temperature energy retention rates and having double discharge voltage plateaus (a first discharge voltage plateau having a higher discharge voltage and a second discharge voltage plateau having a lower discharge voltage) are respectively provided in different regions of the battery pack box. In addition, a battery cell with a higher low-temperature energy retention rate is provided in a region at a lower temperature. Specifically, region division in
The above principle is also applicable to low-temperature energy retention of the battery pack including a k-th battery cell.
It should be noted that specific definition and test method of the discharge capacity proportion corresponding to the second discharge voltage plateau of the first/second/third battery cell refer to the “Related Test” part in the specification.
The discharge capacity of the second discharge voltage plateau having a lower discharge voltage in the battery cell can be adjusted by changing the percentages and types of the supplementary active substances and the proportions of various types of the supplementary active sub stances.
As shown in
A pure lithium iron phosphate/pure lithium nickel cobalt manganate system has good low-temperature discharge performance. Therefore, a battery pack including a pure lithium iron phosphate/pure lithium nickel cobalt manganate system is quite suitable for being used under low temperature.
In this application, the supplementary active substance of which the molecular formula is AxMy(PO4)z can serve as a plateau attenuation buffer agent and can slow down decrease of a discharge voltage when a terminal voltage of a cell during discharging attenuates sharply, thereby prolonging the discharging process and improving the discharging power performance.
In some optional embodiments, a positive electrode active substance of the first battery cell 61 has a gram capacity of 140-198 mAh/g, a positive electrode active substance of the second battery cell has a gram capacity of 137-192 mAh/g, and a positive electrode active substance of the third battery cell has a gram capacity of 134-186 mAh/g.
In this way, the respective gram capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 being within the foregoing ranges allows for substantially same discharge capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 under low temperature, thereby increasing the overall energy retention rate of the battery pack 1 under low temperature.
The gram capacity of the positive electrode active substance of each battery cell refers to an average gram capacity of the positive electrode active substance. For example, the gram capacity can be calculated according to respective gram capacities and mass proportions of lithium iron phosphate and/or lithium nickel cobalt manganate and the supplementary active substance included in the positive electrode active substance.
In some optional embodiments, a theoretical gram capacity of the supplementary active substance is 40-110 mAh/g.
In this way, use of the supplementary active substance of which the theoretical gram capacity is within the foregoing range can ensure each battery cell to have sufficient energy density and can increase the overall low-temperature discharge power of each battery cell and the battery pack.
In some embodiments, the supplementary active substance is one or more selected from Li3V2(PO4)3, Na3V2(PO4)3, K3V2(PO4)3, Li3V(PO4)2, Na3V(PO4)2, K3V(PO4)2, LiMnPO4, NaMnPO4, KMnPO4, Li2VMn2(PO4)3, Na2VMn2(PO4)3, K2VMn2(PO4)3, LiVMn(PO4)2, NaVMn(PO4)2, KVMn(PO4)2, CaV4(PO4)6, LiTi2(PO4)3, NaTi2(PO4)3, KTi2(PO4)3, CaTi4(PO4)6, Li2VTi(PO4)3, Na2VTi(PO4)3, K2VT1(PO4)3, CaVTi(PO4)3, Li3MnTi(PO4)3, Na3MnTi(PO4)3, and K3MnTi(PO4)3.
In some optional embodiments, in the supplementary active substance of which the molecular formula is AxMy(PO4)z, when M is Ti, the element Ti has many variable valences; therefore, the supplementary active substance has an reversible charge/discharge plateau within a voltage region of 2.0-2.6 V; and thus, after a small amount of NTP is mixed, a battery including the supplementary active substance generates a small plateau at 2.0-2.6 V in the end of discharging, slowing down decrease of the voltage and helping to alleviate significant decrease trend of the voltage in a low-charge state, thereby improving the power performance and improving the cold start performance of the system under low temperature.
Similarly, in some optional embodiments, in the supplementary active substance of which the molecular formula is AxMy(PO4)z, when M is V, the discharge voltage plateau is at 1.5-2.1 V.
In some other optional embodiments, in the supplementary active substance of which the molecular formula is AxMy(PO4)z, when M is Mn, the discharge voltage plateau is at 2.3-3.0 V.
M may be a plurality of variable-valence metal elements, and therefore may have a plurality of plateaus.
In some embodiments, in the positive electrode of each k-th battery cell, a mass percentage of the supplementary active substance is 3% to 15% based on a total mass of the positive electrode active substance.
The mass percentage of the supplementary active substance may be 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, or 15%, optionally 3%, 4%, 5%, 6%, 7%, 8%, 9%, or 10%, based on the total mass of the positive electrode active substance.
If the mass percentage of the supplementary active substance is less than 3%, the discharge voltage plateau thereof cannot be shown in a discharge curve, that is, cannot achieve a power increasing effect. If the mass percentage of the supplementary active substance is greater than 15%, the energy retention rate thereof under low temperature is still increased. However, a large percentage thereof not only deteriorates the discharge capacity under room temperature but also results in failure of a more significant increase in overall discharge capacity under low temperature.
In some embodiments, the positive electrode of each first battery cell includes no supplementary active substance, or the positive electrode of each first battery cell includes the supplementary active substance, optionally, a second voltage plateau of the supplementary active substance in the first battery cell is greater than or equal to an overall discharge cut-off voltage of the first battery cell.
In this application, the positive electrode of the first battery cell in the first region may include no supplementary active substance, may partially include the supplementary active substance, or may entirely include the supplementary active substance.
When the first battery cell partially or entirely includes the supplementary active substance, it is advantageous to make the voltage plateau of the supplementary active substance be greater than or equal to the overall discharge cut-off voltage of the first battery cell, because this allows the supplementary active substance to effectively act as a plateau attenuation buffer agent before cutoff of discharging.
In some embodiments, when the respective positive electrodes of the first battery cell to the n-th battery cell include a same positive electrode active substance,
A larger mass percentage of the supplementary active substance for generating the second discharge voltage plateau with a lower discharge voltage indicates a larger discharge capacity proportion corresponding to the second discharge voltage plateau. Therefore, adding a larger percentage of supplementary active substance into the k-th battery cell than the (k−1)-th battery cell in the k-th region at a lower temperature helps to increase the overall low-temperature energy retention rate of the battery pack.
For example, when the respective positive electrodes of the first battery cell, the second battery cell, and the third battery cell use a same type of positive electrode active substance, a configuration that a mass percentage of the supplementary active substance of the third battery cell 63 in the third region R3>a mass percentage of the supplementary active substance of the second battery cell 62 in the second region R2>a mass percentage of the supplementary active substance of the first battery cell 61 in the first region R1 can increase the overall discharge energy and energy retention rate of the battery pack 1 under low temperature.
In some embodiments, the positive electrode of each first battery cell includes no supplementary active substance or includes a same type of supplementary active substance as the second battery cell and the third battery cell.
In actual operation, when the first battery cell (if it uses a supplementary active substance), the second battery cell, and the third battery cell use a same type of supplementary active substance, the manufacturing costs can be reduced, facilitating actual application.
In some embodiments, in the positive electrode of each first battery cell, a mass percentage of the supplementary active substance is 0% to 3% based on a total mass of the active substance of the positive electrode;
Optionally, in the positive electrode of each first battery cell, the mass percentage of the supplementary active substance is 0%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, or 3.0% based on the total mass of the active substance.
Optionally, in the positive electrode of each first battery cell, the mass percentage of the supplementary active substance is 3%, 3.5%, 4.0%, 4.5%, 5.0%, 5.5%, 6.0%, 6.5%, or 7.0% based on the total mass of the active substance.
Optionally, in the positive electrode of each first battery cell, the mass percentage of the supplementary active substance is 7.0%, 7.5%, 8.0%, 8.5%, 9.0%, 9.5%, 10.0%, 11.0%, 12.0%, 13.0%, 14.0%, or 15.0% based on the total mass of the active substance.
In this application, the mass percentages of the supplementary active substances in the first battery cell, the second battery cell, and the third battery cell being within the foregoing ranges can better balance discharge periods of the first battery cell, the second battery cell, and the third battery cell to make the discharge periods be the same as far as possible and can further improve the overall low-temperature energy retention rate and power performance of the battery pack.
In some embodiments, under a temperature below 10° C., 1.6 V≤discharge cut-off voltage of the k-th battery cell≤discharge cut-off voltage of the (k−1)-th battery cell≤2.1 V.
An outer ring (the k-th region) of the battery pack is at a low temperature, and an inner ring (the (k−1)-th region, with respect to the k-th region of the outer ring) is at a high temperature, resulting in a short discharge period and a smaller discharge capacity as well as power performance degradation of the cell in the outer ring. A lower cut-off voltage of the outer ring can allow for release of more energy, compensating for discharge variation of the cell caused by temperature rise in the battery pack, thereby increasing the overall discharge capacity of the battery pack.
In some embodiments, an overall discharge cut-off voltage V1 of the first battery cell is 2.0-2.1 V, an overall discharge cut-off voltage V2 of the second battery cell is 1.7-2.0 V, an overall discharge cut-off voltage V3 of the third battery cell is 1.6-1.9 V, and V1>V2>V3.
In this way, the discharge cut-off voltages of the first battery cell 61, the second battery cell 62, and the third battery cell 63 being set as described above allows the first battery cell 61, the second battery cell 62, and the third battery cell 63 to release substantially same energy under low temperature, thereby increasing the overall energy retention rate of the battery pack under low temperature.
An excessively high charge cut-off voltage or an excessively low discharge cut-off voltage reduces the cycling performance of the battery cell. Under a condition that the charge cut-off voltage is excessively high, the battery cell is over-charged, and under a condition that the battery cell is fully charged, further charging leads to structural changes of a positive electrode material, causing capacity loss; and in addition, oxygen released by decomposition of the positive electrode material has a sharp chemical reaction with an electrolyte, which is possible to cause explosion as a worst result. Under a condition that the discharge cut-off voltage is excessively low, the battery cell is over-discharged, over-discharging causes an increase in internal pressure of the battery cell, and reversibility of positive and negative electrode active substances is reduced, even charging can only recover the reversibility partially, and the capacity attenuates significantly. Deep charge or deep discharge of the battery cell increases loss of the battery cell. The ideal operating state of the battery cell is shallow charge or shallow discharge, which can prolong the service life of the battery cell.
In a battery pack including three regions, an overall discharge cut-off voltage of the first battery cell may be designed according to requirements of a conventional pure lithium iron phosphate or pure lithium nickel cobalt manganate system. To be specific, for a lithium iron phosphate system, the cut-off voltage may be set to be 2.0 V; for a lithium nickel cobalt manganate system, the cut-off voltage may be set to be 2.1 V; an overall discharge cut-off voltage of the second battery cell may be less than a conventional cut-off voltage, in some embodiments a discharge process of the battery surpasses a voltage plateau region of the supplementary active substance, and in this case, reduction of the cut-off voltage and work of an additive platform can both ensure improvement of the power performance and reduce discharge capacity variation of the cell in the inner ring caused by temperature rise; an overall discharge cut-off voltage of the third battery cell is less than the overall discharge cut-off voltage of the second battery cell and greater than 1.6 V, this can ensure full play of the function of the discharge voltage plateau of the supplementary active substance under large power, thereby effectively alleviating voltage attenuation; however, the discharge cut-off voltage cannot be excessively low, and if it is less than 1.6 V, motor power of a vehicle system is limited.
In some optional embodiments, in the first, second, and third battery cells 61, 62, and 63, a difference between a minimum discharge voltage of the first discharge voltage plateau and a maximum discharge voltage of the second discharge voltage plateau is greater than 0.2 V, optionally greater than 0.4 V.
For a battery cell having two discharge voltage plateaus, a larger difference between discharge voltages of the first discharge voltage plateau and the second discharge voltage plateau and a larger discharge capacity of a second discharge voltage of the supplementary active substance indicate a more significant improvement effect provided by the second discharge voltage plateau. If the difference between the minimum discharge voltage of the first discharge voltage plateau and the maximum discharge voltage of the second discharge voltage plateau is less than 0.2 V, the difference between the discharge voltages of the first discharge voltage plateau and the second discharge voltage plateau is smaller, which cannot significantly achieve the foregoing effect provided by the second discharge voltage plateau.
Therefore, optionally, M is Ti or Mn.
The difference between the minimum discharge voltage of the first discharge voltage plateau and the maximum discharge voltage of the second discharge voltage plateau being within the foregoing range, after discharging is performed using the first discharge voltage plateau having a higher discharge voltage, discharging can continue to be performed using the second discharge voltage plateau having a lower discharge voltage, significantly increasing energy that can be released by each battery cell under low temperature, thereby increasing the overall energy retention rate of the battery pack under low temperature.
In some embodiments, a discharge capacity of a single cell of each k-th battery cell is less than a discharge capacity of a single cell of each (k−1)-th battery cell. Optionally, the discharge capacity of the battery cell is a discharge capacity measured at a temperature below 10° C.
In this application, respective constituent units of the first battery cell, the second battery cell, and the third battery cell are referred to as “single cell”.
In some optional embodiments, a discharge capacity of the single cell of the third battery cell 63<a discharge capacity of the single cell of the second battery cell 62<a discharge capacity of the single cell of the first battery cell 61. To be specific, optionally, the “discharge capacity of the single cell of the first battery cell 61”, the “discharge capacity of the single cell of the second battery cell 62”, and the “discharge capacity of the single cell of the third battery cell 63” refer to discharge capacities obtained by respectively measuring the single cell of the first battery cell 61, the single cell of the second battery cell 62, and the single cell of the third battery cell 63 under a same charge/discharge condition at 25° C. before the first battery cell 61, the second battery cell 62, and the third battery cell 63 are assembled into a battery pack.
In this way, making the discharge capacities of the respective single cells of the first battery cell 61, the second battery cell 62, and the third battery cell 63 satisfy the above relationship, especially making the discharge capacities of the first battery cell 61, the second battery cell 62, and the third battery cell 63 measured at a temperature below 10° C. satisfy the above relationship can further increase the overall energy retention rate of the battery pack under low temperature.
In some optional embodiments of this application, under a condition that a supplementary active substance containing no lithium is used, respective negative electrodes of the first battery cell 61, the second battery cell 62, and the third battery cell 63 can be supplemented with lithium. In this way, the respective negative electrodes of the first battery cell 61, the second battery cell 62, and the third battery cell 63 being supplemented with lithium can compensate for deficiency of lithium ions caused by adding the supplementary active substance into the positive electrode active substance, such that a total amount of effective lithium ions of the battery cell are not reduced, thereby ensuring the energy density of the battery cell.
Various well-known methods can be used for supplementing lithium for the negative electrodes. For example, the following methods can be used: a lithium supplementing apparatus is used to supplement lithium for a coated cold-pressed negative electrode plate; a lithium strip conveying structure in the apparatus is configured to convey a lithium strip; a matrix conveying structure is configured to convey the negative electrode plate; the lithium strip and the negative electrode plate are rolled; and after rolled, the lithium strip is attached to a surface of the negative electrode plate, implementing lithium supplement for the negative electrode. The lithium supplement for the negative electrode can improve initial coulombic efficiency of the battery.
In this application, the number of the first battery cell and the number of the k-th battery cell are not limited and are determined based on factors such as temperature distribution determined according to application scenarios, a simulation method and the like as well as a battery pack process.
A second aspect of this application provides a method for arranging battery pack. The battery pack includes a battery pack box and a battery cell accommodated in the battery pack box. The method includes the following steps.
The internal space of the battery pack box includes one or more first regions and/or k-th regions.
A positive electrode of each k-th battery cell includes a positive electrode active substance. The positive electrode active substance includes the following substances:
Electric Apparatus
A third aspect of this application provides an electric apparatus. The electric apparatus includes the battery pack according to the first aspect of this application. The battery pack may be used as a power source of the electric apparatus or an energy storage unit of the electric apparatus. The electric apparatus may include a mobile device (for example, a mobile phone or a notebook computer), an electric vehicle (for example, a battery electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf vehicle, or an electric truck), an electric train, a ship, a satellite system, an energy storage system, or the like, but is not limited thereto.
For the electric apparatus, a battery cell or a battery pack may be selected according to requirements for using the electric apparatus.
The following describes examples of this application. The examples described below are illustrative and only used for explaining this application, and cannot be construed as limitations on this application. Examples whose technical solutions or conditions are not specified are made in accordance with technical solutions or conditions described in literature in the field or made in accordance with product instructions. The reagents or instruments used are all conventional products that are commercially available if no manufacturer is indicated.
1. Preparation of First Battery Cell
(1) Preparation of Positive Electrode Plate
A positive electrode active substance lithium iron phosphate, conductive carbon, and a binder polyvinylidene fluoride (PVDF) were dispersed in a solvent N-methylpyrrolidone (NMP) and mixed to uniformity, with a mass ratio of the lithium iron phosphate, the conductive carbon and the binder polyvinylidene fluoride being 97.2:0.8:2.0, to obtain a positive electrode slurry. The positive electrode slurry obtained was evenly applied onto a positive electrode collector aluminum foil, followed by drying, cold pressing, slitting, and cutting to obtain a positive electrode plate.
(2) Preparation of Negative Electrode Plate
A negative electrode active material graphite, a conductive agent superconducting carbon black SP, a binder SBR, and a thickener CMC-Na were dispersed in deionized water as a solvent at a mass ratio of 96:1:1:2 and mixed to uniformity to obtain a negative electrode slurry. The negative electrode slurry was evenly applied onto a negative electrode current collector copper foil, followed by drying, cold pressing, slitting, and cutting to obtain a negative electrode plate.
(3) Separator
A polyethylene film was used as a separator.
(4) Preparation of Electrolyte
Ethylene carbonate (EC), dimethyl carbonate (DMC), and diethyl carbonate (DEC) were mixed to uniformity at a volume ratio of 1:1:1 to obtain an organic solvent, and then a fully dried lithium salt LiPF6 was dissolved in the mixed organic solvent to prepare an electrolyte with a concentration of 1 mol/L.
(5) Preparation of Battery Cell
The positive electrode plate, the separator, and the negative electrode plate were sequentially stacked so that the separator was located between the positive electrode plate and the negative electrode plate for separation. Then, the resulting stack was wound to obtain a jelly roll. The jelly roll was placed into an outer package shell and dried. Subsequently, the electrolyte was injected, and processes such as vacuum packaging, standing, formation, and shaping were performed to obtain a first battery cell I−1.
2. Preparation of Second Battery Cell
This was the same operation as the preparation of the first battery cell except that active substances used in step (1) included 95% of lithium iron phosphate and 5% of Li3V2(PO4)3, although the total mass of active substance was not changed.
3. Preparation of Third Battery Cell
This was the same operation as the preparation of the first battery cell except that active substances used in step (1) included 91.5% of lithium iron phosphate and 8.5% of Li3V2(PO4)3, although the total mass of active substance was not changed.
The internal space of the battery pack box was divided into three regions using a simulation method with ANSYS-SCDM software (Beijing Huanzhong Ruichi Technology Co., Ltd.). Specific operations were as follows.
Based on the determination using the foregoing method, when the external temperature was set to be −7° C., the first region had a maximum temperature of 18° C. and a minimum temperature of 11° C., the second region had a maximum temperature of 11° C. and a minimum temperature of 4° C., and the third region had a maximum temperature of 4° C. and a minimum temperature of −3° C.
Referring to
An overall cut-off voltage of the first battery cells was designed to be 2 V, an overall cut-off voltage of the second battery cells was designed to be 1.95 V, and an overall cut-off voltage of the third battery cells was designed to be 1.7 V.
Battery packs were assembled using the same operations as in Example 1, except for the design of types of active substances of the first battery cell, the second battery cell, and the third battery cell, mass percentages of supplementary active substances in the total active substances, and/or cut-off voltages. Details are provided in the following Table 1.
In Table 1, in the column of active substances, the mass percentages of the supplementary active substances were calculated based on a total mass of the active substances (mass of lithium iron phosphate/mass of lithium nickel cobalt manganate+mass of the supplementary active substances).
It should be noted that although the embodiments of this application have included an embodiment in which the internal space of the battery pack box is divided into a first region and a second region and an embodiment in which the internal space of the battery pack box is divided into a first region, a second region, and a third region, the battery pack of this application is not limited to only the cases in which the internal space of the battery pack box is divided into two regions and three regions, but may also applicable to cases in which one or more regions are further provided on an outer side of the third region in addition to the first region, the second region, and the third region, provided that the battery cells provided in the region on the outer side are arranged around the battery cells in the region on the inner side of the third region.
In the case that the internal space of the battery pack box includes more than three regions as described above, the discharge capacity proportion corresponding to the second discharge voltage plateau of the battery cell is higher in a region that is closer to the outer side.
In addition, in a case that the internal space of the battery pack box is in a rectangular shape, four corners of the rectangular shape may serve as an outermost region, and in this region, the discharge capacity proportion corresponding to the second discharge voltage plateau of the battery cell is the highest.
[Performance Test]
1. Discharge Capacity of Single Cell and Discharge Capacity Proportion Corresponding to Second Discharge Voltage Plateau
For the first battery cell, the second battery cell, and the third battery cell in each battery pack prepared in the examples and comparative examples, their respective discharge capacities at 25° C. and −7° C. as well as discharge capacities corresponding to the first discharge voltage plateau and the second discharge voltage plateau at −7° C. were measured using a Newway traction battery test machine (Model BTS-5V300A-4CH), and based on those, the discharge capacity proportions corresponding to the second discharge voltage plateaus of the first battery cell, the second battery cell, and the third battery cell were calculated.
The discharge capacity of the battery cell was measured using a method as follows:
Therefore, at −7° C., a discharge capacity proportion corresponding to the second discharge voltage plateau of the battery cell is C3/C1.
The discharge capacity of a single cell in the following Table 1 is the total discharge capacity C0 discharged by the battery cell as measured at 25° C. in step (4).
2. Power Performance of Battery Pack
The maximum power under −7° C. corresponding to 30 s 20% SOC was tested as follows:
3. Discharge Energy of Battery Pack (at −7° C.) and Total Energy Retention Rate of Battery Pack at −7° C.
For each of the battery packs in the examples and comparative examples, total full discharge energy of the battery pack at 25° C. and total full discharge energy of the battery pack at −7° C. were measured using the Newway traction battery test machine (Model BTS-5V300A-4CH), and a total energy retention rate (%) of the battery pack at −7° C. was calculated by dividing the total full discharge energy of the battery pack at −7° C. by the total full discharge energy of the battery pack at 25° C.
The measurement of the total full discharge energy of the battery pack at 25° C. was performed in accordance with “7.1.2 Capacity and Energy Test at Room Temperature” in GBT 31467.2-2015 Technical Specification for Battery Packs and Systems for High Energy Applications.
The measurement of the total full discharge energy of the battery pack at −7° C. was performed in accordance with “7.1.4 Capacity and Energy Test at Low Temperature” in GBT 31467.2-2015 Technical Specification for Battery Packs and Systems for High Energy Applications. The total full discharge energy of the battery pack at −7° C. is the discharge energy of the battery pack at −7° C. in the following Table 1.
Test results are shown in the following tables.
It can be learned from the results of the foregoing table that in examples 1-12, the first battery cell, the second battery cell, and the third battery cell each have a first discharge voltage plateau and a second discharge voltage plateau; in addition, the discharge capacity proportion corresponding to the second discharge voltage plateau of the third battery cell>the discharge capacity proportion corresponding to the second discharge voltage plateau of the second battery cell>the discharge capacity proportion corresponding to the second discharge voltage plateau of the first battery cell; the discharge capacity of the single cell of the first battery cell>the discharge capacity of the single cell of the second battery cell>the discharge capacity of the single cell of the third battery cell; the battery pack has good results in power and discharge energy at −7° C.; and the total energy retention rate of the battery pack at −7° C. is up to 86.3%-92.5%.
However, in comparative example 1 and comparative example 2, the first battery cell, the second battery cell, and the third battery cell each have one discharge voltage plateau, and the total energy retention rate of the battery pack at −7° C. is only 79.3% and 82.2%. Compared with comparative example 1 or comparative example 2 with the same series of battery cell, examples 1-12 each achieve higher discharge energy, higher battery pack power and higher total energy retention rate.
In example 13, the overall cut-off voltage designed for the third battery cell and the overall cut-off voltage designed for the second battery cell are greater than the overall cut-off voltage of the first battery cell, resulting in relatively large power of the battery pack but relatively low total energy retention rate and relatively low discharge energy of the battery pack at −7° C.
It should be noted that this application is not limited to the foregoing embodiments. The foregoing embodiments are merely examples, and embodiments having substantially the same constructions and the same effects as the technical idea within the scope of the technical solutions of this application are all included in the technical scope of this application. In addition, without departing from the essence of this application, various modifications made to the embodiments that can be conceived by persons skilled in the art, and other manners constructed by combining some of the constituent elements in the embodiments are also included in the scope of this application.
This application is a continuation of International Application No. PCT/CN2022/106429, filed on Jul. 19, 2022, the entire content of which is incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/CN2022/106429 | Jul 2022 | US |
| Child | 18503736 | US |
